TWI496811B - Polyesters for coatings - Google Patents

Description

Film coating polyester

The present invention relates to polyesters which can be prepared from renewable resources and/or recycled materials, as well as to their use and methods for their manufacture.

The use of carboxy-, hydroxy and (meth) acryl-based functional polyesters and their use in adhesives for resins and/or coatings has been extensively discussed.

Most of their raw materials are mainly from non-renewable resources. Non-renewable resources are taken from the earth and cannot be recovered once they are removed.

One sustainable way to respond to certain non-renewable resources is regeneration, which means that the starting material will be recycled from its previous use and then reused.

Polyethylene terephthalate (PET) films or waste bottles have been used in a variety of applications, including polyesters for powder coating.

DD 295,647 is a synthesis of a carboxyl functional polyester for powder coating obtained by reacting a high number average molecular weight PET waste polyacid with a polyol.

DE 1,913,923 discloses a thermosetting polyterephthalate binder which is obtained by mixing a hydroxy-functional polyterephthalate and a carboxy-functional polyterephthalate. Both polyterephthalates are obtained by the glycolytic reaction of PET with alcohols.

Non-renewable resources can also be compensated (partially or completely) by regenerating resources. The industrial demand for renewable resources is driven by environmental inferences that fossil fuels will be depleted.

WO 2008/031592 discloses a process for the manufacture of polyesters starting from a mixture of 1,4:3,6-di-water-L-idoidide and a dicarboxylic acid or a dicarboxylic anhydride. Only coatings made with succinic acid as the sole polyacid and isosorbide as the sole polyol have acceptable flexibility and glass transition temperatures for powder coatings.

In WO 2006/102279, polyesters are produced using 1,4:3,6-di-dehydrated-L-iditol and isosorbide. The reaction temperature described therein is 280 ° C and higher. Polyesters prepared from recycled materials and/or renewable resources and prepared in a simple manner have their continuing need and can be used in a variety of different types of coatings.

Against this background, we now offer terephthalic acid and/or isophthalic acid, ethylene glycol, dihydrohexitol (for example isosorbide) and preferably one or more linear dicarboxylic acids. Part of the polyester.

As used herein, "portion" refers to a monomer unit.

The polyester of the present invention is preferably non-thermoplastic. Preferred are thermoset polyesters, but may also be radiation curable polyesters. The polyester of the present invention can be used as part of a paint binder system, and powder coatings are only one example. However, the polyesters of the invention can also be used in liquid coating compositions. The liquid coating composition of the present invention may be water based or solvent based.

Further, the present invention also provides a process for producing the polyester of the present invention. In particular, there is provided a method of producing a polyester comprising the steps of (1) polyethylene terephthalate and/or polyethylene isophthalate and dihydrohexitol to be subjected to glycolysis, followed by If necessary, (2) may have one or more additional steps, more particularly one or more additional reaction steps. In step (1), in addition to dihydrohexitol (for example isosorbide), one or more other polyols (for example glycerol and/or sorbitol) may be used. Manufactured by the process of the invention are hydroxy- or carboxy-functional polyesters having an average number molecular weight (Mn) of from 300 to 15,000 amps measured by gel permeation chromatography (GPC). The Mn of the polyester is generally at least 350 amps, preferably at least 400 amps, and more particularly at least 550 amps. Mn will generally vary depending on the type and nature of the coating using the polyester, and is typically measured by GPC using polystyrene standards.

Surprisingly, it has been found that di-dehexitol can be incorporated into the terephthalic acid and/or isophthalic acid-containing polyester in a short period of time at moderate temperatures.

In the process of the invention, the sugar solution can be quickly used Chan, KP et al. (1994) in macromolecular (Macromolecules), 27,6371-6375 Method, or Spyros, A. Et al. (1997) Giant The method of the molecule , 30, 327-329, was confirmed by analysis on a phosphorus-based resin by 31P-NMR.

Considering the poor reactivity of the dehydrohexitol and the need for a high reaction temperature in the direct condensation method using the dihydrohexitol, such results are unexpected. The glycolysis is carried out with di-dehydrated hexitol and one or more other polyols selected (e.g., glycerol and/or sorbitol), preferably at a temperature and for a time sufficient to obtain a transesterification reaction. The term "other" in this context refers to a polyol different from the dihydrohexitol.

In the process of the invention, step (1) is preferably carried out at a temperature of from 200 ° C to 260 ° C. The temperature of the whole step (1) is preferably lower than 250 °C. More preferably, the step (1) is carried out at a temperature of from 220 ° C to 240 ° C.

Step (1) of the process of the invention is preferably carried out in the presence of a transesterification catalyst. Possible transesterification catalysts include n-butyltin trioctoate and/or tetra-n-butyl titanate.

In certain instances, a hydroxy functional polymer of the desired molecular weight can be obtained after step (1) of the process of the invention.

However, in most instances, step (1) will be followed by one or more additional steps, in particular one or more additional reaction steps. Such additional steps are preferably such that the polyester has the desired properties such as the desired molecular weight, the degree of condensation desired, and the like. Additional steps may include vacuum, chain elongation, carboxylation, and the like and/or other suitable steps.

In a preferred embodiment of the invention, step (1) in the method is followed by step (2) which comprises the steps of chain elongation and/or carboxylation.

In the process of the invention, by applying reduced pressure (<1 atmosphere) or vacuum (for example 50 mmHg) and/or by previously (in step 1) the hydroxy-functional prepolymer with one or more The acid (preferably one or more linear dicarboxylic acids and, optionally, one or more other polybasic acids) is reacted to give chain elongation.

Ethylene glycol can be distilled off under reduced pressure or vacuum until the desired hydroxyl value is obtained. Alternatively, a reduced pressure or vacuum may be applied to distill a portion of the ethylene glycol followed by a condensation reaction with one or more polybasic acids, preferably one or more linear dicarboxylic acids and, optionally, one or more other polybasic acids.

Depending on whether the (partial) ethylene glycol is first distilled, it will change the weight ratio of the dihydrohexitol to the linear dicarboxylic acid (eg, isosorbide versus succinic acid).

The final weight ratio of didehydrated hexitol to linear dicarboxylic acid (e.g., isosorbide versus succinic acid) is desirably from 0.3 to 2.5, typically from 0.5 to 2, preferably from 0.7 to 1.4. Known Tg values may change and may be adjusted depending on the end use.

If the aim is to have a high Tg value, it is preferred to apply a vacuum first to reduce the hydroxyl number of the hydroxy-functional prepolymer obtained in step (1) of the process of the invention. This is particularly beneficial when the hydroxy- or carboxy-functional polyester of the present invention is converted to a (meth) acryl-based functional polyester in a subsequent reaction step.

In the process of the invention, carboxylation is obtained by reacting a previously obtained hydroxy-functional prepolymer (which in step 1 may be followed by a reduced pressure or vacuum step) with one or more polybasic acids. The linear dicarboxylic acid is preferably used alone or in combination with one or more other polybasic acids.

In a preferred method of the invention, one or more polybasic acids are used for the chain elongation and/or the carboxylation. A preferred polybasic acid which can be used in the chain elongation and/or the carboxylation step is a linear dicarboxylic acid. The linear dicarboxylic acid may be used alone or in combination with one or more other polybasic acids. The term "other" as used herein refers to a polycarboxylate (eg, succinic acid) that is different from the linear dicarboxylic acid used. The polybasic acid for the chain elongation and/or the carboxylation in the step (2) is preferably at least one, and more preferably all of the polybasic acid is a regenerated polybasic acid.

In a particular embodiment of the invention, the chain elongation and/or carboxylation step of the process of the invention may be followed by a step of depressurization (<1 atmosphere) or vacuum (e.g., 50 mm Hg). It is preferred to apply a reduced pressure or a vacuum until the desired degree of condensation is obtained.

Step (2), and particularly the chain elongation and/or carboxylation step therein, is preferably carried out at a temperature of from 120 ° C to 260 ° C, particularly from 200 ° C to 260 ° C. Step (2), and particularly the chain elongation and/or carboxylation step therein, is more preferably carried out at a temperature below 250 °C, more particularly between 220 °C and 240 °C.

The capping of the anhydride can also be accomplished in step 2. For carrying out such a reaction, the reaction temperature in the step 2 is generally between 120 ° C and 240 ° C, preferably between 160 ° C and 200 ° C.

Polyethylene terephthalate and/or polyethylene isophthalate used as a starting material in the process of the invention may comprise the polyethylene terephthalate and/or the polyisophthalate The material (or reactant) of the diformate is provided in the form of a material. This material is preferably a recycled material.

Particularly suitable are materials comprising polyethylene terephthalate, in particular recycled polyethylene terephthalate.

The material comprising recycled polyethylene terephthalate is preferably recycled polyethylene terephthalate, more particularly PET waste.

It is of course also possible to use unrecycled PET (or fresh PET) instead of recycled PET.

The use of polyethylene isophthalate as the reactant in step (1) of the process of the invention is particularly advantageous for improving outdoor durability.

In a specific embodiment of the invention, polyethylene terephthalate is first prepared by direct condensation of ethylene glycol with isophthalic acid and/or dimethyl isophthalate. This polyisophthalic acid ethylene ester is then subjected to a glycolysis step as described in step (1) of the process of the invention. The polyethylene isophthalate can be prepared in the same or in another reactor. Alternatively, recycled polyethylene terephthalate can be used.

Polyethylene terephthalate and/or polyethylene isophthalate are preferably the sole source of ethylene glycol and terephthalic acid and/or isophthalic acid incorporated into the polyesters of the present invention.

The invention also relates to polyesters obtainable by the process of the invention.

In particular, a hydroxy- or carboxy-functional polyester having the following moiety is provided,

(a) terephthalic acid and/or isophthalic acid,

(b) ethylene glycol,

(c) di-dehydrated hexitol, and

(d) one or more linear dicarboxylic acids.

The hydroxy- or carboxy-functional polyester of the present invention may further optionally comprise (e) a portion of one or more other polyols (e1) and/or one or more other polybasic acids (e2).

The other polyol (e1) means a polyol different from the didehydrohexitol. Preferably, the polyol is also different from ethylene glycol. Other polyols (e1) are advantageous in parts other than (b) and (c).

The other polybasic acid (e2) means a polybasic acid different from the linear dicarboxylic acid (d). Preferably, the polybasic acid is also different from terephthalic acid and/or isophthalic acid. Other polybasic acids (e2) are advantageous in parts other than (a) and (d).

The hydroxy- or carboxy-functional polyester of the present invention has an average number molecular weight, measured by gel permeation chromatography (GPC), of from 300 to 15,000 amps, preferably from 350 to 15,000 amps, particularly preferably 500 to 15,000 ear drops.

The Mn of the polyester is generally at least 400 amps. Preferably, Mn is at least 550 ear swabs, more preferably at least 750 ear swallows, and most preferably at least 1100 ear swallows. Preferably, Mn is at most 11,000 ampoules, more preferably at most 8,500 amps, depending on the type of coating used in the polyester. Mn is generally measured by GPC in polystyrene standards.

Mn is typically measured on a 3xPLgel 5 micron Mixed-D LS 300 x 7.5 mm column in GPC in THF (tetrahydrofuran) with a MW ranging from 162 to 377400 g/mole and polystyrene at 40 °C. Standard calibration. The refractive index (RI) is generally used as a detector.

The hydroxy- or carboxy-functional polyester of the present invention is preferably prepared from 5 to 35% by weight of the ethylene glycol moiety (b) based on the total weight of the polyester. The amount of the ethylene glycol moiety in the polyester is preferably at least 10% by weight. The amount of the ethylene glycol moiety in the polyester generally does not exceed 30% by weight.

The hydroxy- or carboxy-functional polyester of the present invention is preferably based on the total weight of the polyester.

(a) 10% by weight to 80% by weight of terephthalic acid and/or isophthalic acid,

(b) 5 to 35% by weight of the ethylene glycol moiety,

(c) 5% by weight to 40% by weight of the di-dehydrated hexitol portion,

(d) 5 to 40% by weight of the linear dicarboxylic acid moiety, and

(e) selected from 0% to 40% by weight of one or more other polyols (e1) and/or one or more other polybasic (e2) moieties.

The hydroxy- or carboxy-functional polyester of the invention preferably comprises at least 30% by weight and preferably up to 60% by weight of a terephthalic acid moiety and/or an isophthalic acid moiety.

The hydroxy- or carboxy-functional polyester of the invention preferably comprises at least 10% by weight and preferably up to 30% by weight of the ethylene glycol moiety.

The hydroxy- or carboxy-functional polyester of the invention preferably comprises at least 10% by weight and preferably up to 30% by weight of the didehydrohexitol moiety.

The hydroxy- or carboxy-functional polyester of the invention preferably comprises at least 10% by weight of a linear dicarboxylic acid moiety and preferably up to 30% by weight of a linear dicarboxylic acid moiety.

The hydroxy- or carboxy-functional polyesters of the invention preferably comprise from 0 to 35 wt%, typically from 0 to 20 wt%, one or more other polyol moieties and/or one or more other polybasic acid moieties.

The weight percentages referred to herein are based on the total weight of the polyester.

The hydroxy- or carboxy-functional polyesters of the present invention are generally derived from materials based on polyethylene terephthalate and/or polyethylene isophthalate, which are present in the presence of dihydrohexitol. If present, it is glycolyzed and further reacted with one or more linear dicarboxylic acids.

In general, in the polyester of the invention, less than 10% by weight of terephthalic acid and/or polyisophthalic acid fraction (a) is derived from dialkyl terephthalate and/or Alkyl isophthalate. Preferably, the percentage is less than 5% by weight. The weight percentages referred to herein are based on the total weight of the polyester. The term "di-dehydrohexitol (c)" used in the synthesis of the hydroxy- or carboxy-functional polyester of the present invention refers to any of the three isomers of di-dehydrohexitol, i.e., isosorbide. Anhydride, 1,4:3,6-di-dehydrate-L-iditol and/or 1,4:3,6-dide-D-mannitol. These three isomers may be used singly or as a mixture of two or three of these isomers.

The dihydrohexitol (c) preferably comprises at least isosorbide, optionally with 1,4:3,6-dide-L-iditol and 1,4:3,6- At least one combination of two de-water-D-mannitol. The second dehydrated hexitol (c) is preferably isosorbide. The didehydrohexitol which is preferably isosorbide may be a regenerated polyol.

The linear dicarboxylic acid (d) used in the synthesis of the hydroxy functional or carboxyl functional polyester of the present invention is preferably a linear aliphatic dicarboxylic acid which may be selected from the group consisting of succinic acid, adipic acid, glutaric acid, and glycol. Acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, and selected from, for example, Empol 1018 or Pripol Dimer diacid such as 1013. Preferred is succinic acid, especially succinic acid derived from renewable resources.

The other polyol (e1) used in the synthesis of the hydroxy- or carboxy-functional polyester of the present invention is preferably selected from the group consisting of neopentyl glycol, diethylene glycol, propylene glycol, 1,3-propanediol, and 1,4-butane. Alcohol, 2,3-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,3-propanediol, 2-B Base, 2-butyl-1,3-propanediol, 1-ethyl-2-methyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, hydrogenated bisphenol A, Neopentyl glycol hydroxymethyl trimethylacetate, glycerol, sorbitol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and selected from, for example, SPEZIOL Dimer diol such as 1075. Preferred are sorbitol and/or glycerol and/or 1,3-propanediol, more particularly sorbitol and glycerol.

Particularly suitable is glycerol. Dimer diols are also preferred, particularly dimer diols derived from renewable resources.

The other polybasic acid (e2) used in the synthesis of the hydroxy- or carboxy-functional polyester of the present invention is preferably selected from the group consisting of fumaric acid, maleic acid, itaconic acid, citraconic acid, and methylidene. Aenedioic acid, phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, citric acid, tartaric acid, partial benzene Tricarboxylic acid, pyromellitic acid or the corresponding anhydride (any of the above acids).

The hydroxy- or carboxy-functional polyester of the present invention preferably has an acid value or a hydroxyl value of 10 to 310 mg KOH/g. The acid value or hydroxyl value is preferably at least 15 mg KOH/g, more preferably at least 20 mg KOH/g. The acid value or hydroxyl value is preferably at most 200 mg KOH/g, usually at most 150 mg KOH/g, more preferably at most 100 mg KOH/g, depending on the nature of the coating using the polyester.

Preferred hydroxy- or carboxy-functional polyesters of the invention are characterized by a glass transition temperature (Tg) of less than 120 ° C, according to ASTM D3418, by a differential scanning thermal analyzer at a heating gradient of 20 ° C per minute. The measurement is preferably carried out below 100 ° C, preferably below 80 ° C. If the polyester is used for powder coating, the Tg is preferably at least 40 ° C, more preferably at least 45 ° C, most preferably at least 50 ° C. In the liquid coating composition, the polyester is generally used having a Tg of at least -100 ° C, preferably at least -50 ° C, more preferably at least -20 ° C.

Preferred hydroxy- or carboxy-functional polyesters of the invention have a Brookfield (cone/plate) viscosity of 50 mPa.s at room temperature (e.g., 25 °C) and 15,000 mPa at 200 °C, as measured by ASTM D4287-88. .s. The Brookfield (cone/plate) viscosity at room temperature (e.g., 25 ° C) is preferably at least 500 mPa.s, more preferably at least 700 mPa.s. The Brookfield (cone/plate) viscosity at 200 ° C is preferably at most 12,000 mPa.s, more preferably at most 10,000 mPa.s.

The hydroxy functional and/or carboxyl functional polyester of the present invention is preferably an amorphous polyester.

The following are some of the best ways to make the hydroxy- or carboxy-functional polyesters of the present invention:

The hydroxy- or carboxy-functional polyester of the present invention is preferably recovered from polyethylene terephthalate and di-dehexitol (preferably isosorbide) and optionally one or more other polyols. The transesterification reaction (sometimes expressed as glycolysis) (such as glycerol/or sorbitol) is obtained. Another example of such other polyols is 1,3-propanediol. In the obtained hydroxy-functional prepolymer, a linear dicarboxylic acid, preferably succinic acid, and optionally one or more other polybasic acids are added. The polycondensation is continued, first at atmospheric pressure, followed by under reduced pressure until the correct polyester properties are obtained.

When starting with (recovered) polyethylene terephthalate, the dedehydrated hexitol is placed together with another polyol (preferably glycerol) with a stirrer, inert gas (for example nitrogen) ) In a conventional reactor with an inlet, a thermocouple, a distillation column connected to a water-cooled condenser, a water separator and a vacuum connection tube, and heated to 160 °C. Among them, it is preferred to contain a transesterification catalyst such as n-butyltin trioctoate or tetra-n-butyl titanate.

Once at 160 ° C, the (recovered) polyethylene terephthalate was gradually added with stirring while raising the temperature to 230 ° C. Once 230 ° C was reached and the contents of the entire reactor were easily converted to a liquid phase, stirring was continued for another 3 hours under a nitrogen atmosphere. If desired, in order to reduce the ethylene glycol content of the hydroxy-functional prepolymer, a vacuum step can be applied until the assumed hydroxyl value is reached. The temperature of the reactor contents is then cooled to 160 ° C to 200 ° C, and a linear dicarboxylic acid, preferably succinic acid, is added, optionally with the addition of one or more other polybasic acids. A condensation catalyst such as n-butyltin trioctoate can be added. The reactor contents were again heated to 230 °C. The contents of the reactor were then stirred at 230 ° C for an additional 2 hours under atmospheric pressure and a nitrogen atmosphere. A vacuum is then applied, and then the amount of water formed during the reaction and the properties of the obtained polyester, such as hydroxyl value, acid value, molecular weight or viscosity, are measured.

During the polyesterification reaction or at the end thereof, a color stabilizer of 0 to 1% by weight of the reaction reactant may be selectively added, for example, a phenol antioxidant such as IRGANOX 1010 (Ciba) or a phosphonite and phosphite type stabilizer, such as tributyl phosphite.

When the (thermosetting) hydroxy functional or carboxy functional polyester of the present invention is still in a molten state, a crosslinking catalyst can be selectively added. These selected catalysts are added to accelerate cross-linking of the thermoset composition during hardening. Examples of such catalysts include amines (e.g., 2-phenylimidazoline), phosphines (e.g., triphenylphosphine), ammonium salts (e.g., tetrabutylammonium bromide or tetrapropylammonium chloride), and phosphonium salts (e.g., bromination). Ethyl triphenyl hydrazine, tetrapropyl hydrazine chloride, tin catalyst (such as dibutyltin dilaurate), bismuth catalyst (such as neodymium neodecanoate) or zinc catalyst (such as zinc octoate). Other blocking or latent catalysts such as those described in US Pat. No. 5,134,239, or WO 0,137,991, or the coatings described in US Pat. No. 6,274,673 or EP 1,348,742. These catalysts are preferably used in an amount of from 0 to 5% by weight based on the weight of the polyester.

The didehydrohexitols, linear dicarboxylic acids, other polybasic acids and/or other polyols used in the preparation process of the invention (any of the above specific examples) may be derived from renewable resources.

In a particular embodiment of the invention, the polyester of the invention is a reactant comprising (or comprising) recycled polyethylene terephthalate and/or recycled polyethylene isophthalate, and It may be prepared from a plurality of polyols and/or polybasic acids, wherein at least one of the polyols and/or polybasic acids is derived from a renewable resource.

In a particular embodiment of the invention, the polyester of the invention is prepared from a reactant comprising (or comprising) recycled polyethylene terephthalate and from one or more polyols and/or polyacids, wherein at least A polyol and/or polyacid is derived from a renewable resource. Preferably all of the polyols and/or polyols are taken from renewable resources.

The polyol and/or polyacid obtained from the renewable resources is preferably derived from a raw material such as vegetable oil, starch, cellulose/pulp, sugar, natural fiber and/or other botanical raw materials.

The hydroxy functional and/or carboxyl functional polyesters of the present invention can be used in thermosetting coating compositions and/or radiation hardening coating compositions. The thermosetting coating composition may be a powder coating composition or a liquid coating composition. The liquid coating composition of the present invention may be water based or solvent based. One aspect of the invention pertains to such coating compositions.

Preferred thermosetting coating compositions of the present invention comprise at least one hydroxy functional group of the present invention and/or at least one carboxy functional polyester, and a crosslinking agent having a functional group reactive with the polyester functional group. Depending on the type of hardener used, it may be desirable to have an acid catalyst.

The thermosetting coating composition of the present invention can provide a coating exhibiting excellent flow characteristics and excellent flexibility upon application and hardening at a temperature between room temperature (e.g., 25 ° C) and 200 ° C. For powder coating, the hardening temperature is usually between 100 ° C and 200 ° C.

In the liquid coating composition, a polyester polyol is generally used. When considering the use of a solvent-based coating composition, the polyester solution used is preferably characterized by a solids mass fraction of at least 60%, preferably at least 70%, more preferably at least 75% (determined in accordance with DIN EN ISO 3251) ). The mass fraction of the solid is preferably not more than 99%.

The polyester solution is preferably characterized by a dynamic viscosity (determined at 23 ° C, according to DIN EN ISO 3219) of 50 to 35,000 mPa.s. The viscosity is preferably at least 500 mPa.s, more preferably at least 1000 mPa.s, most preferably at least 1500 mPa.s. The viscosity is preferably at most 30,000 mPa.s, more preferably at most 25,000 mPa.s, and most preferably at most 20,000 mPa.s.

The polyester used has a hydroxyl number (OH) (determined in accordance with DIN EN ISO 4629) on the solid resin preferably between 10 and 310 mg KOH/g, more preferably between 10 and 300 mg KOH/g. The OH value is preferably at least 50 mg KOH/g, more preferably at least 80 mg KOH/g, most preferably at least 100 mg KOH/g. The OH value is preferably at most 250 mg KOH/g.

The polyester polyols used in the liquid coating compositions are typically low molar mass polyester polyols. The low molar mass polyester polyol used can be chemically or physically modified by the reaction, for example by reaction with an isocyanate compound or a compound containing an oxirane group. Other possible modifications include the incorporation of low molar mass urea derivatives. These polyester polyols may also be an essential component of a (grafted) acrylate polymer, as described in US Pat. No. 6,258,897, the disclosure of which is incorporated herein by reference.

In the liquid coating composition, the polyester of the present invention may be partially substituted with an acrylic resin.

Therefore, the liquid coating composition comprises at least one acrylic resin and at least one polyester resin, and the ratio of the polyester resin:acrylic resin is between 4:1 and 2:1, preferably between 3.5:1 and 2.5:1. The best is between 3.2:1 and 2.2:1.

The liquid coating composition used in the method of the present invention preferably further contains at least one hardener. Suitable hardeners are hardeners known in the art.

Possible hardeners (or crosslinkers) include (block or non-block) polyisocyanates, amine based resins, phenolic resins, polycarboxylic acids and anhydrides thereof (see, for example, US 6,258,897). Non-block polyisocyanates can be used to harden at moderate or room temperature. Blocked polyisocyanates, as well as polycarboxylic acids and anhydrides thereof, are particularly suitable for hardening at elevated temperatures.

The amine based resin is a preferred hardener (or curing agent), more particularly a urea resin, a melamine resin and/or a benzoguanamine resin. These are respectively etherified urea-, melamine- or benzoguanamine-formaldehyde condensation products. Particularly preferred are melamine resins, especially high solids methylated melamine resins such as hexamethoxymethyl melamine resin.

As used herein, the term "high solid" refers to a solid mass fraction of at least 70%, especially at least 75%, preferably at least 95%. Suitable hardeners are, for example, hexamethoxymethyl melamine resins having a solids mass fraction of 98% or more. Other preferred embodiments include high imine based resins having a solids mass fraction ranging from 78% to 82%.

When an amine-based resin is used as the hardener, it is preferred to add an acid catalyst. In a particular embodiment of the invention, the liquid coating composition used further comprises an acid catalyst.

A fully alkylated amine-based resin usually requires a strong acid catalyst such as CYCAT 4045, partially alkylated and high imine based resins typically require only a weak acid catalyst. Urea and acetylene urea resins respond better to strong acid catalysts.

Examples of possible catalysts include amine blocked p-toluenesulfonic acid (pTSA), dimethyl pyrophosphate (DMAPP), dodecylbenzenesulfonic acid (DDBSA), and dinonylnaphthalenedisulfonic acid (DNNDSA). Preferably, the catalyst is an amine blocked p-toluenesulfonic acid, such as ADDITOL. VXK 6395 and CYCAT 4045.

In the liquid coating composition, the mass fraction of the resin is preferably between 10% and 90%. The mass fraction of the resin is preferably at least 20%, more preferably at least 50%. The mass fraction of the resin is preferably at most 85%, more preferably at least 80%. In the liquid coating composition, the mass fraction of the hardener is preferably between 5% and 70%. The mass fraction of the hardener is preferably at least 10%, more preferably at least 12%. The mass fraction of the hardener is preferably at most 40%, more preferably at least 25%.

The ratio of the mass fraction of the resin to the hardener is preferably between 6:1 and 1:1, especially between 5:1 and 2:1.

The mass fraction of the acid catalyst used in the liquid coating composition is preferably between 0% and 10%, especially between 0.1% and 10%. The mass fraction of the selected catalyst is preferably at least 0.3%. The mass fraction of the selected catalyst is preferably not more than 8%.

Examples of solvents suitable for use in the present invention, particularly preferred oligoester polyols and/or acrylic resins include aliphatic hydrocarbons, cycloaliphatic hydrocarbons and aromatic hydrocarbons such as alkylbenzenes such as xylene, toluene; esters such as acetic acid. Ethyl ester, butyl acetate, acetate with longer alcohol residue, butyl propionate, amyl propionate, ethylene glycol, monoethyl ether acetate, corresponding methyl ether acetate and propylene glycol methyl ether acetate; Ethers such as ethylene glycol monoethyl ether, monomethyl or monobutyl ether; glycols; alcohols; ketones such as methyl isoamyl ketone and methyl isobutyl ketone; lactones, and mixtures of such solvents. Other solvents that may be used include the reaction product of a lactone with a glycol or an alcohol. Particularly preferred are dimethyl ester (e.g. Santosol ^TM DME-1, of adipic, glutaric and succinic acid dimethyl ester) and a mixture of S-100 (aromatic hydrocarbon solvent from HuaLun chemical) of. Butanol can help stabilize the storage of paint. The mass fraction of the solvent selected for use in the liquid coating composition is generally between 0% and 50%. The mass fraction of the solvent to be used is preferably at least 5%, more preferably at least 10%. The mass fraction of the solvent to be used is preferably at most 40%, more preferably at most 30%.

The liquid coating composition of the present invention may further contain pigments and/or colorants and/or fillers. Examples of the filler include talc, mica, kaolin, chalk, quartz powder, slate powder, various cerium oxides, cerium salts, and the like. The mass fraction of the selected pigment and/or colorant and/or filler in the liquid coating composition is preferably between 0% and 50%, more preferably between 2% and 40%.

The liquid coating composition resin can be applied to the substrate by any suitable coating method. Examples thereof are brushing, dip coating, flow coating, roll coating or knife coating, but in particular spraying.

The latter hardens after the substrate is coated with the liquid coating composition. Hardening, i.e., cross-linking, can be accomplished by any suitable means known to those skilled in the art. For the purposes of the present invention, the liquid coating material is typically cured in a temperature range of from 20 ° C to 160 ° C (preferably from 23 ° C to 140 ° C) for a period of, for example, 5 minutes to 10 days, more particularly 15 minutes. 120 minutes.

In a specific embodiment of the method of the invention as hereinbefore described, further comprising the step of converting said hydroxy-functional polyester or carboxy-functional polyester to a (meth) acryl-based functional polyester, more particularly (methyl) A propylene thiol-functional blocked polyester. In the present invention, the term "(meth)acrylinyl" is taken to include both an acryloyl group and a methacrylamidyl compound or derivative, and a mixture thereof. The invention also includes polyesters obtained (or obtainable) from the process of the invention.

One aspect of the invention pertains to such (meth)acrylenyl-functional polyesters obtained or produced from the hydroxy- or carboxy-functional polyesters of the invention. The (meth) propylene fluorenyl functional polyester of the present invention, particularly a (meth) propylene fluorenyl functional blocked polyester, is particularly suitable for use in radiation hardening and/or heat hardening coating compositions, optionally Combined with one or more ethylenically unsaturated co-hardeners.

Converting the carboxyl and hydroxy functional polyesters of the present invention to a (meth) acrylonitrile terminated polyester can be accomplished by reacting a diisocyanate with a hydroxyalkyl (meth) acrylate and a hydroxyl end group of the polyester; The glycidyl methacrylate is reacted with the hydroxyl end group of the polyester. Alternatively, a (meth)acrylonyl terminated polyester is obtained by reacting a hydroxyl group of (meth)acrylic acid with a polyester.

The hydroxyalkyl (meth) acrylate used for the reaction with the diisocyanate in the above reaction is preferably selected from the group consisting of hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl 3-(meth)acrylate, 2- , 3- and 4-(hydroxy) hydroxybutyl acrylate.

In the above reaction, the diisocyanate for reacting with the hydroxyalkyl (meth) acrylate and the hydroxyl group-containing polyester is preferably selected from the group consisting of 1-isocyanato-3,3,5-trimethyl-5-isocyanide. Acid methyl-cyclohexane (isophoric acid diisocyanate, IPDI), tetramethyl xylene diisocyanate (TMXDI), hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, 4, Technical mixture of 4'-diisocyanate dicyclohexylmethane, 4,4'-diisocyanate diphenylmethane, 2,4-diisocyanate diphenylmethane, and the above diisocyanate Homolog, 2,4-diisocyanate toluene and its technical mixture with toluene 2,6-diisocyanate, and α,α'-dimethyl-m-isopropylbenzyl isocyanate (TMI) Copolymerization product.

Conversion of a hydroxy or carboxy functional polyester to a (meth) propylene fluorenyl functional polyester can be carried out in a large number of processes or in a solvent such as toluene in the presence of any known catalyst such as p-toluenesulfonic acid. In progress.

A particularly preferred method of producing the (meth) propylene fluorenyl functional polyester of the present invention is as follows:

When the polycondensation reaction previously described is complete, the hydroxy functional or carboxyl functional polyester of the present invention in a molten state in the reactor is cooled to between 100 ° C and 160 ° C and is 0.01 to 1% by weight relative to the polyester. The proportion is added with a radical polymerization inhibitor such as a thiodiphenylamine or hydroquinone type inhibitor, and the nitrogen inlet is substituted for the nitrogen.

When starting from the hydroxy-functional polyester of the present invention, a substantially equivalent amount of hydroxyalkyl (meth)acrylate is added. When all of the hydroxyalkyl (meth) acrylate was added, an equal amount of diisocyanate was slowly added to the mixture. A catalyst for the hydroxyl/isocyanate reaction can be optionally used. Examples of such catalysts include those catalysts listed above for accelerating the crosslinking reaction. The preferred amount of these catalysts relative to the weight of the polyester is from 0 to 1% by weight.

Alternatively, a substantially equal amount of (meth)acrylic acid is added to the hydroxy-functional polyester of the present invention. The reaction is preferably carried out in 10% by weight to 50% by weight of a solvent such as toluene, cyclohexane and/or heptane at a temperature of from about 80 ° C to about 120 ° C and from 0.1% by weight to 5% by weight of the catalyst. This is done in the presence of a sulfonic acid or sulfuric acid, which can be rinsed off after the reaction is complete.

In addition to this, when starting from the carboxyl functional polyester of the present invention, a substantially equivalent amount of glycidyl (meth)acrylate is added. A catalyst for an acid/epoxy reaction can be selectively used. Examples of such catalysts include those catalysts listed above for accelerating the crosslinking reaction. The preferred amount of these catalysts relative to the weight of the polyester is from 0.05 to 1% by weight.

The degree of progress of the reaction is generally determined by measuring the properties of the obtained polyester, such as hydroxyl value, acid value, free (meth)acrylic acid propyl acrylate or (meth) propionic acid hydroxyalkyl ester unsaturation and / Or content.

The (meth)acrylonyl functional polyester of the present invention obtained is preferably characterized by an unsaturation of from 0.15 to 5.00, usually from 0.15 to 4.00, and a double bond of milliequivalent per gram of polyester. The degree of unsaturation is preferably from 0.35 to 3.00, more particularly from 0.35 to 2.50, and the double bond is equivalent per gram of polyester. The (meth) propylene fluorenyl functional polyester of the present invention preferably has a telechelic unsaturation ranging from 0 to 5.0, typically from 0 to 2.5, more preferably from 0 to 2 meq/g of polyester.

Preferred (meth) acryl-based functional polyesters for use in powder coatings having a number average molecular weight (Mn), measured by gel permeation chromatography (GPC), of at least 400 amps, generally at least 550 ear drops, preferably at least 850 ear swabs, and more preferably at least 1200 ear swallows.

Preferred (meth)acryloyl-functional polyesters for use in radiation-curing coating compositions have a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of at least 350 amps, generally At least 400 ear swabs, preferably at least 550 ear swabs, and more preferably at least 750 ear swallows.

Still another aspect of the invention is directed to a coating composition comprising at least one (meth)acryl oxime functional polyester of the invention, and preferably further comprising at least one ethylene unsaturated oligomer and/or monomer. The ethylenically unsaturated oligomer is preferably a polyfunctional (meth) acrylate oligomer. By polyfunctional is meant herein an oligomer having at least two unsaturated groups selected from the group consisting of acrylate and/or methacrylate groups.

The coating composition may be a radiation hardening coating composition or a thermosetting coating composition.

Various types of coating compositions can be prepared using the polyesters of the present invention. The coating composition can be any thermosetting and/or radiation hardening composition comprising at least one of the hydroxy-functional polyesters, carboxyl-functional polyesters, and/or (meth)acryl-based functional polyesters previously described. Thermosetting coating compositions, especially thermosetting powder coating compositions, are only one particular example.

The invention also provides a polyester resin comprising at least one polyester of the invention. Likewise, the polyester may be any of the polyesters previously described, that is, hydroxy-functional polyesters, carboxyl-functional polyesters, and/or (meth)acryl-based functional polyesters as previously described.

In a particular embodiment of the invention, the hydroxy-functional polyester, carboxyl-functional polyester and/or (meth)acryl-based functional polyester resin of the invention optionally comprises from 0 to 10% by weight of an acrylic copolymer. As described in WO 2009/095460. The acrylic copolymer is preferably added in an amount of at least 0.5% by weight, more preferably at least 1% by weight, based on the weight of the polyester. The amount of such an acrylic copolymer added is preferably at most 5% by weight, more preferably at most 3% by weight, based on the weight of the polyester.

The acrylic copolymer is typically added during the melt of the polyester of the invention, during synthesis or at the end of its synthesis, before or during discharge.

Thermosetting coating compositions (especially thermosetting powder coating compositions) are only one aspect of the invention.

When the resin of the present invention is used in a thermosetting coating composition, it is preferably compounded with at least one crosslinking agent, and thus the binder constituting the coating formulation can be selected from the (thermosetting) coating composition when it is radiation hardenable. There is one or more co-hardeners such as ethylenically unsaturated monomers and/or oligomers, as described later.

One embodiment of the present invention is directed to a thermosetting coating composition comprising at least one polyester of the present invention and further comprising at least one crosslinking agent reactive with the polyester functional groups. In particular, such thermosetting coating compositions comprise at least one hydroxy-functional polyester of the invention and/or at least one carboxy-functional polyester of the invention and/or at least one (meth)acryl-based functional polyester of the invention.

The crosslinking agent which can be combined with the polyester of the present invention is preferably selected from the group consisting of polyepoxy compounds, compounds containing β-hydroxyalkylguanamine or polyisocyanate compounds and mixtures thereof.

Preferred polyepoxides are solid at room temperature and contain at least two epoxy groups per molecule. Particularly preferred is triglycidyl isocyanurate, such as Araldite, which is commercially available. PT810 commodity; a blend of diglycidyl terephthalate and triglycidyl trimellitate, such as the commercial Araldite PT910 and Araldite PT912; and bisphenol A based epoxy resin, such as the product Araldite GT 7004 or DER 692.

It is also possible to use a monomer derived from glycidyl (meth)acrylate, at least one alkyl (meth)acrylic acid monomer and (optionally) one or more different from an alkyl (meth)acrylic monomer or (methyl) A glycidyl-containing acrylic copolymer of an ethylene monounsaturated monomer of a glycidyl acrylate monomer, as described in WO 91/01748.

Particularly preferred are β-hydroxyalkylguanamines containing at least one, preferably two, bis β-hydroxyalkyl guanamine groups. Such compounds are described, for example, in US-A-4,727,111.

Examples of the polyisocyanate crosslinking compound include those which are based on the ε-caprolactone block of isophorone diisocyanate, which are commercially available from Vestagon. B1530, Ruco NI-2 and Cargill 2400; or a compound based on ε-caprolactone block toluene-2,4-diisocyanate, available from commercially available Cargill 2450; and phenolic block hexamethylene diisocyanate.

Another block polyisocyanate compound which can be used is an adduct of a 1,3-diazetidine-2,4-dione dimer of diisocyanate diisocyanate and a diol, wherein The ratio of the NCO group to the OH group at the time of formation of the adduct is about 1:0.5 to 1:0.9, and the molar ratio of the diazetidinedione to the diol is from 2:1 to 6:5. In the adduct, the free isocyanate group content is not more than 8% by weight, and the adduct has a molecular weight of about 500 to 4,000 and a melting point of about 70 to 130 °C. Such an adduct can be obtained from the market item - Vestagon BF1540.

On the other hand, when considering a thermosetting coating composition based on an unsaturated polyester (particularly based on the (meth)acryloyl-functional polyester of the present invention), it can be added to this formulation. A polymerization initiator such as an azobis-based initiator or a peroxide. Examples of such starters include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), lauryl peroxide, and second-peroxide Butyl, bis(4-t-butylcyclohexyl)peroxydicarbonate, tert-butylperoxide (2-ethylhexanoate), methyl ethyl ketone peroxide and benzammonium peroxide .

Alternatively, one or more co-hardeners selected from ethylene-unsaturated monomers and/or oligomers may also be added, and particularly suitable examples are described later.

Still another aspect of the invention is directed to a radiation hardenable coating composition comprising at least one (meth) propylene fluorenyl functional polyester of the invention and at least one ethylenically unsaturated monomer and/or oligomer.

When used in radiation-curing coating compositions, the (meth)acryl-based functional polyesters of the present invention are preferably formulated with one or more ethylenically unsaturated monomers and/or oligomers to form a binder for the coating formulation. . The binder may further comprise at least one photoinitiator and, optionally, at least one photoactivator. The photoinitiator is generally added when the radiation hardening composition of the present invention is hardened by UV irradiation or actinic irradiation, but when it is used, for example, by electron beam hardening, it is not required to be added.

The photoinitiator useful in the present invention is selected from the group of users who are often used for this purpose.

Suitable photoinitiators which can be used are, for example, aromatic carbonyl compounds such as diphenyl ketone and its alkylated or halogenated derivatives, hydrazine and its derivatives, thioxanthone and its derivatives, benzoin ethers. , aromatic or non-aromatic alpha-diketone (alphadione), diphenylethylenedione dialkyl acetal, acetophenone derivatives and phosphine oxides.

Particularly suitable photoinitiators are, for example, 2,2'-diethoxyacetophenone, 2-, 3- or 4-bromoacetophenone, 2,3-pentanedione, hydroxycyclohexylbenzophenone , benzaldehyde, benzoin, diphenyl ketone, 9,10-dibromofluorene, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4,4'-dichlorodiphenyl ketone, Xanthone, thioxanthone, diphenylethylenedione dimethyl acetal, diphenyl (2,4,6-trimethylbenzyl)phosphine oxide, and the like.

A photoactivator such as tributylamine, 2-(2-aminoethylamino)ethanol, cyclohexylamine, diphenylamine, tritylamine or an amino acrylate, for example, a secondary amine, may optionally be used. Addition products (such as dimethylamine, diethylamine, diethanolamine, etc.) and polyol polyacrylates (such as trimethylolpropane, 1,6-hexanediol diacrylate, etc.).

The radiation hardening coating composition of the present invention may contain 0 to 15 parts by weight, preferably 0.5 to 8 parts by weight, of the photoinitiator for 100 parts by weight of the binder.

The radiation hardening composition of the present invention preferably contains up to 20% by weight, more preferably up to 10% by weight, of an ethylenically unsaturated monomer and/or an ethylenically unsaturated oligomer, preferably selected from the group consisting of three (2) Triacrylate and trimethacrylate of hydroxyethyl)isomeric cyanurate, epoxy acrylate and methacrylate formed by the reaction of an epoxy compound (for example, bisphenol A with acrylic acid or methacrylic acid) A diglycidyl ether), a urethane acrylate and an amine group formed from an organic di- or polyisocyanate with a hydroxyalkyl acrylate or a hydroxyalkyl methacrylate and optionally a mono- and/or polyhydroxylated alcohol Formate methacrylate (for example, a reaction product of hydroxyethyl (meth) acrylate with toluene diisocyanate or isophorone diisocyanate), acrylic acrylate or methacrylic acid acrylate, for example, (methyl) A reaction product of acrylic acid and a copolymer containing a propylene group which is obtained by copolymerization of an acrylic monomer such as n-butyl methacrylate and methyl methacrylate.

The radiation hardening composition of the present invention preferably contains up to 50% by weight, more preferably up to 30% by weight, and still more preferably up to 10% by weight of ethylenically unsaturated (hydrogenated) polyphenylene oxide and/or acrylic acid. Copolymers and/or semi-crystalline polyesters and/or polyesters decylamine and/or polyurethanes.

Examples of dilute monomers suitable for use include: β-carboxyethyl acrylate, butyl (meth)acrylate, methyl (meth)acrylate, isobutyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl ester, cyclohexyl (meth)acrylate, n-hexyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)acrylate, n-lauryl (meth)acrylate, ( Methyl) octyl/decyl acrylate, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonyl phenol ethoxylate, 2-(2-ethoxylated) Ethyl ethoxy) ethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, neon decyl methacrylate (meth) acrylate, N-vinyl pyrrolidone, 1 ,6-hexanediol diacrylate (HDDA), pentaerythritol triacrylate (PETIA), trimethylolpropane triacrylate (TMPTA), dipropylene glycol diacrylate (DPGDA), phenyl epoxypropyl ether acrylic acid Esters, and their (meth)acrylated ethoxylated or/and propoxylated derivatives (eg (meth)acrylated ethoxylated or/and propoxylated trimethylolpropane, glycerol, neopentyl glycol and/or pentaerythritol) .

Yet another aspect of the invention relates to a coating composition that can be cured by heat and radiation. For dual hardening applications, a combination of both hot and radiation hardened coating formulations can be added.

The coating composition of the present invention may further comprise additional materials including rheology agents such as Rheocin R (Ashland), AC 540A (Honeywell), Disparlon PL-525 (Kusumoto), flow regulators such as Resiflow PV5 (Worlee), Modaflow (Cytec Surface Specialities), Acronal 4F (BASF); pigment dispersants such as Solplus D510 (Lubrizol) or Disperbyk-180 (BYK); leveling agents such as those required by WO 2009/095460, such as benzoin ( BASF) and so on.

A particular embodiment of the invention relates to thermoset or radiation hardenable powder coating compositions, particularly thermosetting powder coating compositions. If the coating composition is a powder coating composition, the binder may also contain various additional materials that are often used in powder coatings and varnishes. Examples thereof are wear resistant additives such as Additol P 950 (Cytec Surface Specialities); UV light absorbers such as Tinuvin 900 (Ciba); hindered amine light stabilizers represented by Tinuvin 144 (Ciba); other stabilizers such as Tinuvin 312 And 1130 (Ciba); antioxidants such as Irganox 1010 (Ciba) and stabilizers from the phosphonite or phosphite type.

While most or all of the additives are typically added to the powder coating formulation, they may also be added while the polyester is still molten, during synthesis, or at the end of the synthesis or exiting the reactor.

It can be made into both colored systems and transparent lacquers.

In this coating composition (particularly the powder coating composition of the present invention), many kinds of dyes and pigments can be used. Examples of useful pigments and dyes are: metal oxides such as titanium dioxide, iron oxide, zinc oxide, etc.; metal hydroxides; metal powders; sulfides; sulfates; carbonates; silicates such as ammonium citrate; ; talc; kaolin; iron blue; barite; lead blue; organic red; organic dark red.

The present invention also provides a process for preparing the powder coating composition of the present invention. The components of the powder coating composition of the present invention may be mixed by dry blending in a mixer or a stirrer such as a tumbler mixer. The premix is generally homogenized in a single-axis extruder (such as BUSS-Ko-Kneter) or a biaxial extruder (such as PRISM or APV) at a temperature of 60 ° C to 100 ° C. After cooling, the extrudate is then ground into a powder having a particle size between 10 and 150 microns. The powder coating composition of the present invention can be sprayed onto a substrate using a powder spray gun such as an electrostatic CORONA spray gun or a TRIBO spray gun. On the other hand, known powder precipitation methods such as fluidized bed technology can also be used. After precipitation, it is generally preferred to heat the powder to a temperature between 100 ° C and 250 ° C for a period of time, for example about 0.5 to 30 minutes, so that the granules can flow and fuse together on the surface of the substrate. A smooth, uniform, continuous coating film is formed. When a radiation hardening powder is used, the coating in a molten state is hardened by UV irradiation or by irradiation with an electron beam. For the application of the double-hardening, in order to obtain further hardening, the hardened coating film can be post-heated, in particular, a region (hidden region) which cannot be completely cured by irradiation.

The coating composition of the present invention, particularly the powder coating composition of the present invention, can be applied to a considerable amount of substrates, for example, paper, cardboard, wood, fabric, plastic, such as polycarbonate, poly(methyl). Acrylate, polyolefin, polystyrene, poly(vinyl chloride), polyester, polyurethane, polyamide, copolymer, such as acrylonitrile butadiene styrene (ABS) or cellulose acetate Ester butyrate, etc.; and applied to metals of different nature, such as copper, aluminum, steel, and the like.

The coating prepared from the powder coating composition of the present invention can provide a coating which exhibits excellent flow characteristics and excellent flexibility.

The coating composition of the invention comprising at least one of the polyesters of the invention is particularly suitable for use in coil-and food-contact applications, particularly can coating, including the interior of coated metal cans, particularly those containing alcoholic beverages. . This is especially true for powder coating compositions. The liquid coating compositions of the present invention are also well suited for these applications, particularly for coil and can coating.

The polyesters of the present invention, particularly the hydroxy-functional polyesters of the present invention, can also be used in the preparation of ethylenically unsaturated polymers such as polyurethane polymers. A water-dispersible polyurethane polymer is preferred.

Typically such water-dispersible polyurethane polymers are prepared from an isocyanate-terminated polyurethane prepolymer.

Such isocyanate-terminated polyurethane prepolymers are generally formed by reacting at least the following ingredients:

(i) a molar excess of polyisocyanate;

(ii) a hydroxyl terminated polyester of the present invention;

(iii) an organic compound selected comprising at least two isocyanate-reactive groups different from (ii);

(iv) An isocyanate-reactive compound containing a hydrophilic group to enable the prepolymer to be dispersed in an aqueous medium to produce a salt directly or after reaction with a neutralizing agent.

The polyisocyanate (i) used in the preparation of the isocyanate-terminated polyurethane prepolymer of the present invention may be an aliphatic, cycloaliphatic or aromatic polyisocyanate which is well known in the art. It is usually preferred to use a diisocyanate or an adduct thereof. The total amount of the polyisocyanate (i) used is generally from 10 to 60% by weight, preferably from 20 to 50% by weight, more preferably from 30 to 40% by weight, based on the weight of the polyurethane polymer.

The optional organic compound (iii) containing at least two isocyanate-reactive groups used or prepared to form a cyanate-terminated polyurethane prepolymer may be a polyester polyol, a polyether polyol, a polycarbonate Ester polyol, polyacetal polyol, polyester decylamine polyol or polythioether polyol. Preferred are polyester polyols, polyether polyols and polycarbonate polyols. The compound preferably has a number average molecular weight of between 400 and 5,000.

The isocyanate-reactive compound (iv) generally includes a compound containing a dispersed anionic group such as a sulfonate or carboxylate group, which allows the polyurethane prepolymer to be self-dispersed in water.

Particularly preferred are anionic salt functional groups selected from the group consisting of -COOM and -SO3M groups, preferably -COOM groups, wherein M represents an alkali metal or ammonium, a tetraalkylammonium or a tetraalkylguanidino group. The anionic salt side group content of the polyurethane polymer can vary over a considerable range, but it needs to be sufficient to provide the water dispersibility required for the polyurethane. In general, the amount of these anionic salt-based compounds contained in the polyurethane polymer is from 1 to 25%, preferably from 4 to 10% by weight based on the weight of the polyurethane polymer. Alternatively, the hydrophilic pendant group capable of dispersing the polyurethane prepolymer in water is an acid group, which is preferably selected from the group consisting of a carboxylic acid, a sulfonic acid, and/or a phosphate group.

The preparation of the isocyanate-terminated polyurethane prepolymer can be carried out in a conventional manner by subjecting a stoichiometric excess of the organic polyisocyanate (i) to the compounds (ii) to (iv) under substantially anhydrous conditions. The reaction is carried out at a temperature between 50 and 120 ° C, preferably between 70 and 95 ° C, until the reaction between the isocyanate group and the isocyanate-reactive group is substantially complete. If necessary, 5 to 40% by weight, preferably 10 to 20% by weight, of a solvent may be added to assist the reaction to lower the viscosity of the prepolymer. Suitable solvents are solvents which do not react with isocyanate groups, such as ketones, esters and guanamines such as N,N-dimethylformamide, N-cyclohexylpyrrolidine and N-methylpyrrolidone, which may be used alone. Use or in the form of a mixture. Preference is given to ketones and esters having a relatively low boiling point, such as acetone, methyl ethyl ketone, diisopropanone, methyl isobutyl ketone, methyl acetate and ethyl acetate.

If desired, the preparation of the isocyanate-terminated polyurethane prepolymer can be carried out in the presence of any known catalyst suitable for the preparation of polyurethanes, such as amines and organometallic compounds.

During the preparation of the isocyanate-terminated polyurethane prepolymer, the ratio of reactants (i) to (iv) is generally equivalent to the ratio of isocyanate groups to isocyanate-reactive groups, about 1.1: From 1 to about 4:1, preferably from 1.3:1 to 3:1. Any acid group which may be present in the polyurethane prepolymer is preferably converted to an anionic salt group by neutralizing the group before or at the same time as the aqueous dispersion of the prepolymer is prepared. group. Dispersion methods for polyurethane prepolymers are well known to those skilled in the art and are rapidly agitated with a high shear rate type mixing head. The polyurethane prepolymer is preferably added to the water with vigorous stirring, or water is added to the prepolymer with stirring.

Examples of suitable neutralizing agents include volatile organic bases and/or non-volatile bases well known in the art. The total amount of these neutralizing agents must be calculated in accordance with the total amount of neutralized acid groups. They are preferably used in an amount of from 5 to 30% by weight, more preferably from 10 to 20% by weight.

The obtained isocyanate functional prepolymer may also be reacted with an active hydrogen-containing chain extender (v) and/or an unsaturated compound (vi) having at least one unsaturated function in the molecule, such as a propenyl group. a methacryl or allyl functional group, and at least one nucleophilic functional group capable of reacting with an isocyanate. Among them, propylene functionality is preferred because of its high reactivity. Particularly suitable are acrylic or methacrylic esters having a polyol in which at least one of the hydroxyl functions is still unbound, for example, having from 1 to 20 carbon atoms in the alkyl group and having a linear or branched structure (methyl) ) hydroxyalkyl acrylate. Examples of monounsaturated compounds are hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate, and the like. Examples of polyunsaturated compounds are trimethylolpropane diacrylate, dipropylene glycol diacrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate and their polyethoxylate, polypropylene oxide or block copolymers. Things. It is preferred to provide those products in which the final composition has non-irritating properties. Particularly suitable for this purpose are monounsaturated products and ditrimethylolpropane triacrylate.

The use of the acrylated chain terminator (vi) allows it to be completely converted during the reaction with the available isocyanate groups of the polyurethane prepolymer, i.e., the mole number of the isocyanate group relative to the hydroxyl group is preferred. Between 1.0 and 2.0. In very special cases, this ratio may also be lower than 1. In particular, it is possible to add an unhydroxylated polyunsaturated compound which does not react with the prepolymer isocyanate group to increase the crosslinking density of the polymer after irradiation, based on the weight of the prepolymer, in an excess of 5 -50%, preferably between 20-30%.

The aqueous polyurethane polymer dispersion can be dispersed by a polyurethane prepolymer (selectively in the form of a solution in an organic solvent) which is blocked with an isocyanate and/or an ethylenically unsaturated group. It is prepared in an aqueous medium and optionally in the aqueous phase by elongation of the chain of the prepolymer with an active hydrogen-containing chain extender (v). The active hydrogen-containing chain extender (v) which can be used for the reaction with the isocyanate-terminated polyurethane prepolymer can be a water-soluble aliphatic, alicyclic, aromatic or heterocyclic group. A primary or secondary polyamine having up to 80 carbon atoms, preferably up to 12 carbon atoms, or water. In the latter case, a fully reacted polyurethane polymer can be obtained which does not contain residual free isocyanate groups.

The chain extension reaction is generally carried out at a temperature between 5 ° C and 90 ° C, preferably 20 ° C to 50 ° C. When the chain extender is not water, such as a polyamine, it may be added to the prepolymer before or after the prepolymer containing the side chain acid group neutralizing agent is dispersed in the aqueous medium. According to another specific embodiment, the prepolymer can be elongated to form a polyurethane, while being dissolved in an organic solvent, followed by adding water to the polymer solution until the water becomes a continuous phase, and then The solvent is removed by distillation to form a pure aqueous dispersion of the polyurethane polymer. Preferably, the amine concentration gradient localization is avoided by first forming an aqueous polyamine solution for chain elongation and slowly adding the solution to the polyurethane prepolymer dispersion.

One aspect of the invention pertains to ethylenically unsaturated polymers, particularly the water-dispersible polyurethanes previously described.

Still another aspect of the invention relates to a radiation hardening composition, more particularly an aqueous radiation hardening composition comprising at least one ethylenically unsaturated polymer, in particular comprising at least one water dispersible polyurethane of the invention. Coating compositions containing such polymers exhibit good flexibility and stain resistance and solvent resistance.

When considering a liquid radiation-curing coating composition, one or more photoinitiators known in the art may be added, whether solvent-free, solvent-based or water-dispersible. The photoinitiator is preferably used in a concentration of from 0.1 to 10%.

The radiation hardening composition of the present invention may also contain an inhibitor such as hydroquinone, methylhydroquinone, monomethylhydroquinone, tert-butylhydroquinone, di-tert-butylhydroquinone, and/or thiodiphenylamine. The amount of the inhibitor used is preferably from 0 to 0.5% by weight.

The radiation hardening composition can be applied by any conventional method, including dip coating, spray coating, electrostatic coating, film coating, curtain coating, vacuum coating, roll coating, knife coating, or by engraving a cylinder, etc., applied to any Substrates, including wood, fabric, paper, plastic, fiberboard, cardboard, glass, fiberglass, ceramics, cement, leather, metal, etc., for industrial or residential use.

The hardening resin can be applied to the substrate at any suitable temperature, usually at 10 to 80 ° C, preferably at room temperature.

After the substrate is coated with the radiation hardening composition, it is hardened. If solvent or water is present, it can be evaporated before or during the hardening process. Hardening, i.e., polymerization, can be carried out using any suitable means known to those skilled in the art. Radiation hardening can be accomplished using UV light or ionizing radiation such as gamma rays, X-rays or electron beams. In the process of the invention, electron beams and UV radiation, in particular UV radiation, are preferred. When the composition of the invention is hardened by an accelerated electron beam, it is not necessary to use a photoinitiator because this type of radiation itself produces sufficient energy to generate free radicals and indeed enables hardening to proceed very quickly.

The invention still further provides an article that is partially or completely coated with the coating composition of the invention.

The invention still further provides a method of partially or completely coating an article with a coating composition, the method comprising the steps of: applying a coating composition to at least one surface of the article, followed by hardening the applied coating composition . The coating used may be a powder coating composition which may be a thermosetting or radiation hardenable coating composition, more particularly a thermosetting powder coating composition.

As mentioned previously, the coating composition used may also be a liquid thermosetting or radiation hardenable coating composition.

These examples are intended to be illustrative, and not restrictive. Unless otherwise indicated, the parts referred to in the context of the description and the examples refer to parts by weight.

Example 1 step 1

A mixture of 215.0 parts of isosorbide, 19.8 parts of glycerol and 1.0 part of tetra-n-butyl titanate was placed in a conventional four-necked round bottom flask. The contents of the flask were heated to a temperature of about 160 ° C while stirring, which was carried out under nitrogen. Thus, 572.0 parts of recycled polyethylene terephthalate was slowly added while stirring, and the mixture was gradually heated to a temperature of 230 °C.

After three hours at 230 ° C, the reactor was cooled to 160 °C.

Step 2

A mixture of 245.4 parts of succinic acid together with 1.0 part of tributyl phosphite and 1.0 part of butyl stannic acid was added to the hydroxy-functional prepolymer of step 1. At the same time, the mixture was gradually heated to 230 °C. After two hours at a temperature of 230 ° C, a vacuum of 50 mm Hg was gradually applied until the following characteristics were obtained:

AN=35.2 mg KOH/g

OHN = 5.5 mg KOH / gram

Brfld ^200°C = 7380 mPa.s

Tg ^quenching (DSC, 20 ° / min) = 56 ° C

Step 3

Under a nitrogen atmosphere, 5.0 parts of ethyltriphenyl bromide was added to the carboxyl functional polyester maintained at 230 ° C while stirring. The reactor was emptied after 30 minutes of mixing.

Example 2 step 1

In the same manner as in Example 1, 128.4 parts of isosorbide, 21.5 parts of glycerin and 1.0 part of tetra-n-butyl titanate and 738.7 parts of recycled polyethylene terephthalate were used at a temperature of 230 ° C. The reaction was carried out for 3 hours. A vacuum was then gradually applied to distill 70.0 parts of ethylene glycol to obtain a hydroxy-functional prepolymer having a hydroxyl value of 100 mg KOH/g. The reaction mixture was then cooled to 160 °C.

Step 2

Next, 131.9 parts of succinic acid was added to 1.0 part of the hydroxy-functional prepolymer maintained at 160 ° C together with 1.0 part of tributyl phosphite and 1.0 part of butyl stannic acid. At the same time, the mixture was gradually heated to 230 °C. After two hours at a temperature of 230 ° C, a vacuum of 50 mm Hg was gradually applied until the following characteristics were obtained:

AN=53.1 mg KOH/g

OHN = 5.2 mg KOH / gram

Brfld ^200°C =1650 mPa.s

Tg ^quenching (DSC, 20 ° / min) = 54 ° C

Step 3

In the manner of Example 1, 5.0 parts of ethyl bromide ethyl bromide was added to the carboxyl functional polyester maintained at 230 °C.

Example 3 step 1

In the same manner as in Example 1, 204.8 parts of isosorbide, 10.7 parts of glycerin and 1.0 part of tetra-n-butyl titanate and 620.2 parts of recycled polyethylene terephthalate were used at a temperature of 230 ° C. The reaction was carried out for 3 hours until a hydroxyl value of 200 mg KOH/g was obtained. The reaction mixture was then cooled to 160 °C.

Step 2

Next, 215.7 parts of succinic acid together with 1.0 part of tributyl phosphite and 1.0 part of butyl stannic acid were added to the hydroxy-functional prepolymer of the step 1 maintained at 160 °C. At the same time, the mixture was gradually heated to 230 °C. After two hours at a temperature of 230 ° C, a vacuum of 50 mm Hg was gradually applied until the following characteristics were obtained:

AN=26.7 mg KOH/g

OHN = 7.6 mg KOH / gram

Brfld ^200°C = 8710 mPa.s

Tg ^quenching (DSC, 20 ° / min) = 58 ° C

Step 3

In the manner of Example 1, 5.0 parts of ethyl bromide ethyl bromide was added to the carboxyl functional polyester maintained at 230 °C.

Example 4 step 1

In the same manner as in Example 1, 210.2 parts of isosorbide, 15.2 parts of glycerin and 1.0 part of tetra-n-butyl titanate and 650.8 parts of recycled polyethylene terephthalate were used at a temperature of 230 ° C. The reaction was carried out for 3 hours until a hydroxyl value of 220 mg KOH/g was obtained. The reaction mixture was then cooled to 160 °C.

Step 2

Next, 168.0 parts of succinic acid was added together with 1.0 part of tributyl phosphite and 1.0 part of butyl stannic acid to the hydroxy-functional prepolymer of the step 1 maintained at 160 °C. At the same time, the mixture was gradually heated to 230 °C. After two hours at a temperature of 230 ° C, a vacuum of 50 mm Hg was gradually applied until the following characteristics were obtained:

AN=6.0 mg KOH/g

OHN=32.5 mg KOH/g

Brfld ^200°C = 9300 mPa.s

Tg ^quenching (DSC, 20 ° / min) = 58 ° C

Step 3

In the manner of Example 1, 6.7 parts of dibutyl dilaurate was added to the hydroxy-functional polyester maintained at 200 °C.

Example 5 step 1

In the same manner as in Example 1, a mixture of 229.1 parts of isosorbide, 10.2 parts of glycerol and 1.0 part of tetra-n-butyl titanate and 595.3 parts of recycled polyethylene terephthalate were used at a temperature of 230 ° C. The reaction was carried out for 3 hours, and then the reaction mixture was cooled to 160 °C.

Step 2

101.9 parts of succinic acid was then added along with 1.0 part of tributyl phosphite and 1.0 part of butyl stannic acid to the hydroxy-functional prepolymer of step 1 maintained at 160 °C. At the same time, the mixture was gradually heated to 230 °C. After two hours at a temperature of 230 ° C, a vacuum of 50 mm Hg was gradually applied until the following characteristics were obtained:

AN=40 mg KOH/g

OHN = 3 mg KOH / gram

Brfld ^200°C = 7200 mPa.s

Step 3

The carboxyl functional polyester was cooled to 150 ° C and 0.9 parts of di-tert-butyl hydroquinone and 4.9 parts of ethyl bromide were added. Next, 71.7 parts of glycidyl methacrylate (30 minutes) was slowly added while stirring under an oxygen atmosphere. After 1 hour from the end of the addition, a (meth)acrylonitrile-based unsaturated polyester having the following characteristics can be obtained:

AN=1 mg KOH/g

OHN = 39 mg KOH / gram

Unsaturation = 0.6 meq/g

Brfld ^200°C = 5400 mPa.s

Tg ^quenching (DSC, 20 ° / min) = 57 ° C

Examples 6 to 9

The polyesters of Examples 1 to 3 were formulated with Araldite GT 7004, thus constituting a binder.

The polyester of Example 4 was formulated with Vestagon B 1530 to form a binder, and the white powder formulation (1) was as follows:

Adhesive 690.6 parts

Kronos 2310 296.0 copies

Modaflow P6000 9.9

Benzoin 3.5 servings

Example 10

The polyester of Example 1 was formulated with Primid XL552 to form a binder, and the brown powder formulation (2) was as follows:

Adhesive 783.3 parts

Bayferrox 130 44.4 copies

Bayferrox 3950 138.0 copies

Carbon Black FW2 10.9

Modaflow P6000 9.9

Benzoin 3.5 servings

Example 11

The polyester of Example 5 was formulated so that the powder formulation (3) was as follows:

750.0 parts of the polyester of Example 5

Kronos 2310 250.0 servings

Irgacure 2959 12.5 servings

Irgacure 819 12.5 servings

Modaflow P6000 10.0 parts

These powders were prepared by first dry blending the different ingredients and then homogenizing the melt using a PRISM 16 mm L/D 15/1 biaxial extruder at an extrusion temperature of 85 °C. The extrudate was ground in an Alpine 100UPZ (from Alpine) mill and then sieved to obtain particles having a powder diameter between 10 and 110 microns.

The prepared powder was electrostatically deposited on a cold-rolled steel at a voltage of 60 kV using a GEMA-Volstatic PCG 1 spray gun to a thickness of 0.8 μm, and a hardened coating film having a film thickness of about 80 μm was obtained in this manner.

Examples 6 to 10

The plates containing the coatings obtained from the polyesters of Examples 1 to 4 were then transferred to a ventilation oven where the coatings of Examples 6 to 10 were allowed to harden for 15 minutes at a temperature of 180 °C.

Example 11

The plate containing the coating obtained from the polyester of Example 5 was then subjected to a melting step in a medium wavelength infrared/convection oven (Triab) at a temperature of 140 ° C for a period of approximately 3 minutes and then at 160 watts / cm. The ultraviolet light emitted by the doped and/or 160 watt/cm medium pressure mercury vapor UV lamp (Fusion UV Systems) was irradiated at a total UV-dose of 4000 mJ/cm 2 .

The resulting hardened coating film was subjected to conventional testing. The results obtained are listed in the table below, where:

Column 1: Example number of formulation/coating film

Column 2: Numbering of the polyester example

Column 3: Polyester/hardener ratio

Column 4: Indicates 60° gloss, measured in accordance with ASTM D523

Column 5: indicates direct impact strength (DI) and reverse impact strength (RI) obtained in accordance with ASTM D2794. The highest impact strength that does not cause the film to rupture is recorded in kilograms per centimeter.

Column 6: Represents Erichsen's slow embossing in accordance with ISO 1520. The highest penetration depth that does not cause the film to rupture is recorded in millimeters.

Column 7: Resistance to MEK, which corresponds to the number of double (back and forth) frictional movements of the cotton sheet impregnated with MEK without adversely affecting the appearance of the surface of the cured film.

As is clear from the above table, the powder coating containing the polyester of the present invention exhibits excellent flexibility (DI/RI), which is confirmed by the T-bend test. The coatings obtained from the polyesters of Examples 1 to 5 were subjected to a 0-T bending test. The coating of Example 10 was also sent to Q-UV accelerated weathering test in accordance with ASTM G53-88 (Standard Practice for Operation of Devices for Contact with Light and Water - Luminous UV/Condensation Type - for Contact with Non-Metallic Materials) The machine (Q-Panel) was tested.

The plate for Q-UV is a plate of yellow chromate aluminum. At this point, the plate was subjected to intermittent condensation (4 hours at 40 ° C), and the catastrophic effect of sunlight was simulated by a luminescent UV-B lamp (313 nm, I = 0.75 watts / square meter / nanometer) ) (4 hours at 50 ° C). After 200 hours of treatment with QUV-B, the value of 60° gloss dropped to 50% of its original value.

Examples 12 to 13

The polyester-polyol was synthesized in the following manner: in a conventional four-necked round bottom flask equipped with a stirrer, a distillation column connected to a water-cooled condenser, a nitrogen inlet, and a thermocouple connected to a temperature regulator, A mixture of ethylene glycol (DEG), isosorbide (isoS) and esterification catalyst (300-500 ppm Sn, equivalent to 0.15-0.25 wt% Fascat 4102) was heated to 160 °C.

While stirring, the recovered polyethylene terephthalate (PET) was slowly added while the mixture was heated to 230 °C.

After all of the PET had been added, the reaction mixture was maintained at 230 ° C for 2 hours. The reaction mixture was then cooled to about 150 ° C and succinic acid (SA) and isophthalic acid (iPA) were added. After all of the succinic acid and isophthalic acid had been added, the reaction mixture was again heated to 230 °C.

After 2 hours at 230 ° C, a vacuum was gradually applied until 50 mm Hg was reached and maintained until the correct resin characteristics (hydroxyl value and acid value) were obtained.

The polyester-polyols of Examples 12 and 13 were prepared according to the procedure described above:

Example 14

886.08 parts of the polyester of Example 13, 151.90 parts of acrylic acid, 23.1 parts of methanesulfonic acid (70%), 0.8 parts of methyl ether hydroquinone and 521.0 parts of toluene were placed in a stirrer, a thermocouple connected to a temperature regulator, and a gas. The inlet tube was mixed with a vacuum junction and a double glass reactor in an azeotropic distillation column and heated to a temperature of about 120 °C. The esterification reaction is continued until no more water is distilled off. The mixture was then cooled to 60 ° C and an additional 521.0 parts of toluene was added. The mixture was then washed three times with 10% by weight of the reaction mixture and a concentration of 16% by weight of Na ₂ SO ₄ /water solution, and dried by azeotropic distillation. The toluene was then distilled off under a vacuum of about 30 mmHg, and the reaction product was filtered. In the obtained acrylate-terminated polyester, tris(propylene glycol) diacrylate is added in an amount such that the final mixture contains 80% by weight of an acrylate-terminated polyester and 20% by weight of tris(propylene glycol) diacrylate. .

Example 15

211.8 parts of the polyester of Example 12 was diluted in 141.2 parts of metopropyl acetate at room temperature using a Dispermat having a 25 mm diameter dispersion disk at 1200 rpm. Next, 297.1 parts of Kronos 2190 (TiO ₂ pigment) were gradually added to the polyester solution in 5 minutes while stirring at a rate of 1,250 to 1,800 rpm. After the pigment was completely added, the stirring speed was increased to 5,750 rpm for 10 minutes until the size of the pigmented binder was less than 4 microns, which was measured by a Grindometer.

Next, 116.7 parts of a solution of 70.0 parts of the polyester of Example 12 and 46.7 parts of methoxypropyl acetate, and 94.4 parts of Cymel 303 LF (highly methylated melamine crosslinker, from the obtained pigment paste were added from the obtained pigment paste. Cytec), 4.2 parts of Cycat 4040 (crosslinking catalyst based on 40% by weight of p-toluenesulfonic acid in isopropanol from Cytec), 130 parts of metopropyl acetate and 4.4 parts of Additol XL 122N (Flow, wetting and slip promoter from Cytec), while manually stirring.

The obtained pigment formulation was sieved through a 20 micron sieve and then applied to a primed 0.21 mm thick aluminum plate with a 60 micron bulk applicator. After pre-drying for 45 seconds at room temperature, the aluminum plate was transferred to a preheated work table where it was hardened for 30 seconds at 240 ° C (metal temperature). After maintaining at 240 ° C for 30 seconds, the aluminum plate was then rinsed with tap water for quenching and dried for evaluation.

Under the coating thickness of 15 microns, the measured Knoop film hardness is 19.5 kg / mm 2 , the resistance to methyl ethyl ketone is 200 double rubs, the brightness of the 20 ° film gloss is 76% (ASTM D523), Erichsen slow embossing (ISO 1520) is 7.2 mm, and the bending test (ASTM D4145) is 3-4.

As observed with the solvent-based liquid formulation of the polyester of Example 12, the performance of the present invention is comparable to currently available solvent-based coil coating formulations.

In addition, the coating obtained from the formulation of Example 15 has been shown to be stably sterilized by low temperature (at 80 ° C for 30 minutes), and when applied over an aluminum plate, it can be sterilized at 105 ° C for 30 minutes. And when applied over a tin plate, it can be sterilized at 121 ° C for 30 minutes, which is a very general requirement for beverage and food canned coating on the outside.

Example 16

952.4 parts of the acrylate-containing mixture of Example 14 was mixed with 47.6 parts of a photoinitiator blend consisting of 50% by weight of diphenyl ketone and 50% by weight of hydroxycyclohexyl benzophenone (Irgacure 184). The mixture was mechanically stirred for 15 minutes to give a uniform clear coating formulation.

The radiation hardening formulation of Example 16 was then applied over LENETA paper (forming a WA-white pattern) using a 20 micron rod applicator and using a UV light source (medium pressure mercury vapor lamp with a power of 80 watts/cm) Hardening was carried out at a speed of 30 meters per minute, which was assisted by concentrated radiation by a semi-elliptical reflector, and the total dose was 265 millijoules per square centimeter.

The clarified coating obtained has outstanding resistance to 10% aqueous ammonia solution, 50% aqueous ethanol solution and isopropanol. In addition, after hardening at a speed of 20 meters per minute using 5 continuous UV light sources, a free film having a thickness of about 100 microns can be obtained, each of which is a medium pressure mercury vapor lamp having a power of 80 watts/cm. Constructed by a semi-elliptical reflector to help concentrate radiation, and the total dose is 2400 mJ/cm ^ 2 , with a Young's modulus of 23.5 MPa and an elongation at break of 43.5%, which means that the coating has a high degree of Flexible.

Example 17

181.90 parts of 1,3-propanediol, 181.9 parts of isosorbide and 1.50 parts of Fascat 4102 (n-butyltin trioctoate) in a distillation column equipped with a stirrer, connected to a water-cooled condenser, a nitrogen inlet tube, and a temperature The conventional four-necked round bottom flask of the thermocouple coupled to the regulator was heated to 160 °C.

While stirring, 281.55 parts of recovered polyethylene terephthalate (PET) was slowly added while the mixture was heated to 230 °C.

After all of the PET had been added, the reaction mixture was maintained at 230 ° C for 2 hours. The reaction mixture was then cooled to about 150 ° C and 218.05 parts of succinic acid and 83.61 parts of isophthalic acid were added. After all of the succinic acid and isophthalic acid had been added, the reaction mixture was again heated to 230 °C.

After 2 hours at 230 ° C, a vacuum was gradually applied until reaching 50 mmHg, and was maintained until an acid value of 3 mg KOH/g and a hydroxyl value of 165 mg KOH/g were obtained. This polyester monohydric alcohol is then used to prepare a radiation curable polyurethane dispersion.

Example 18

In a double-layer glass reactor equipped with a mechanical stirrer, thermocouple, steam condenser and dropping funnel, 190.0 parts of the polyester of Example 17, 53.2 parts of dimethylolpropionic acid, 24.5 parts of cyclohexane were placed. Methanol, 332.2 parts of tetramethylphenyldimethyl diisocyanate, 2.3 parts of Irganox 245, 4.6 parts of Tinuvin 328, 4.6 parts of Tinuvin 622 and 0.6 parts of acetone in butyl laurate (10%) as a reaction catalyst. The reaction mixture was heated to 90 ° C with stirring, and this condensation method was maintained until the isocyanate content reached 1.67 meq/g. The polyurethane prepolymer was cooled to 70 ° C, 0.18 parts of 4-methoxyphenol was dissolved in 314.9 parts of pentaerythritol triacrylate (PETIA), and added to the vessel. The reaction mixture was maintained at 70 ° C and this capping process was maintained until the isocyanate content reached 0.42 meq/g. Next, 40.6 parts of triethylamine as a neutralizing agent was added to the warmed prepolymer until homogeneous. With vigorous stirring and away from the phase transfer point, 1722 parts of water at room temperature was charged to the reactor.

After vigorous stirring for about 5 minutes, a stable polymer dispersion was obtained, but stirring was continued for one hour. The product was filtered through a 100 micron screen. It has a dry content of 32.9%, a pH of 7.8, a particle size of 54 nm and a coarse particle content of <100 mg/l. It contains no solvents.

The dispersion was formulated with 1.5% Irgacure 500 (photoinitiator sold by Ciba). It was applied to a white PVC and hardened under 80 watts/cm of UV light, which aided in concentrated radiation by a semi-elliptical reflector at 5 meters per minute and a total dose of 1100 millimeters. Joules per square centimeter are used for the conditions.

The obtained coating film proved to have good flexibility and stain resistance, and excellent resistance to 50% ethanol solution and isopropyl alcohol.

Claims (18)

A hydroxy- or carboxy-functional non-thermoplastic polyester comprising the following: (a) terephthalic acid and/or isophthalic acid, (b) ethylene glycol, (c) didehydrohexitol, and d) One or more linear dicarboxylic acids wherein the polyester has an average number molecular weight, measured by gel permeation chromatography, from 400 to 15,000 amps. The polyester of claim 1 is based on the total weight of the polyester and comprises: (a) 10% by weight to 80% by weight of terephthalic acid and/or isophthalic acid, (b) 5 to 35% by weight of the ethylene glycol moiety, (c) 5 to 40% by weight of the didehydrohexitol moiety, (d) 5 to 40% by weight of the linear dicarboxylic acid moiety, And (e) from 0% to 40% by weight of one or more other polyols (e1) and/or one or more other polybasic (e2) moieties. A polyester according to claim 1 or 2 wherein the dihydrohexitol is isosorbide. A polyester according to claim 1 or 2, wherein the average number of molecular weights is from 550 to 15,000 ampoules. a (meth)acryloyl-functional polyester, as claimed in the patent application The polyester of any one of items 1 to 4 is prepared. A coating composition comprising the polyester according to at least one of the items 1 to 5 of the patent application. An article partially or completely coated with a coating composition as in claim 6 of the scope of the patent application. A method of making a non-thermoplastic polyester comprising the steps of (1) polyethylene terephthalate and/or polyethylene isophthalate with didehydrohexitol for glycolysis, followed by (2) If desired, there may be one or more additional steps wherein the polyester produced is a hydroxy or carboxy function and has an average number of molecular weights, measured by gel permeation chromatography, from 400 to 15,000 amps. The method of claim 8, wherein the step (2) comprises a chain elongation and/or carboxylation step of the previously obtained hydroxy-functional polyester. The method of claim 9, wherein one or more linear dicarboxylic acids are used to effect elongation and/or carboxylation of the chain. The method of any one of claims 8 to 10, wherein the polyethylene terephthalate and/or polyethylene isophthalate used in the step (1) comprises the poly pair A form of a material of ethylene phthalate and/or polyethylene isophthalate. The method of claim 11, wherein the material is a recycled material. For example, the method of claim 12, wherein the recycled material is back Polyethylene terephthalate was collected. The method of any one of claims 8 to 10, wherein the dihydrohexitol is an isosorbide obtained from a raw material. The method of any one of claims 8 to 10, further comprising converting the obtained hydroxy-functional polyester or carboxyl-functional polyester into a (meth) acryl-based functional polyester. The method of claim 15, wherein the (meth)acrylonitrile-terminated polyester is obtained by reacting a diisocyanate with a hydroxyalkyl (meth)acrylate and a terminal hydroxyl group of the carboxyl functional polyester, or It is obtained by reacting (meth)acrylic acid with a terminal hydroxyl group of a carboxyl functional polyester. The method of claim 15, wherein the (meth)acrylonitrile-terminated polyester is obtained by reacting a terminal carboxyl group of a glycidyl (meth)acrylate and a carboxyl functional polyester. The method of claim 8, wherein the average number of molecular weights is from 550 to 15,000 otots.